Biomineralization • The processes by which organisms form minerals – The control by many organisms over mineral formation distinguishes these process from abiotic mineralization • Until the 1980s the field was known as calcification reflecting the large number of biologically formed calcium-containing minerals Calcium • Calcium is the cation of choice for most organisms comprising 50% of known biominerals – Calcium phosphate, carbonate, oxalate and other mineral types • 25 % of the minerals are non-crystalline • 25 % of biogenic minerals are phosphates • Calcium carbonates are the most abundant biogenic minerals Calcium Carbonate • Eight known polymorphs – Seven crystalline and one amorphous – Three are pure calcium carbonate; aragonite, calcite, and vaterite – Two contain one water molecule per calcite; monohydrocalcite and amorphous calcite – Calcium carbonate hexahydrate 1 Other Biominerals • Calcium phosphate – Bone – Teeth • Celestite- Acantharians • Barite- Loxedes • Silica-Diatoms Radiolarians • Iron Oxides-magnetic bacteria – Iron teeth-limpets and chitins Uses • Skeletons • Gravity Sensors- otoliths • Lenses- Trilobites • Vaterite- Ascidians, some inner ears of fish, repair in molluscs • Amorphous calcium carbonate-storage of Ca in plants Biominerals • Biominerals meet the criteria for being true minerals but they can possess other characteristics – Unusual external morphologies; how do organisms do this – Actually composites of crystals separated by organic material 2 Saturation • In order for a mineral to form, the product of the activity of the elements in the solution must exceed the thermodynamic solubility 2- IAP = αCa . αCO3 > Ksp α = γm γ = activity coefficient Definitions SI = IAP/Ksp If SI =1 Solution is at saturation Seawater is ~ 4 with respect to aragonite Seawater •Seawater – Ca 410 ppm 10 mM 2- –CO3 12 ppm 0.2 mM – Mg 1200 ppm 55 mM Ksp (aragonite) = 10-8.301 Ksp (calcite) =10-8.481 Ksp (HMC) =10(-8.21 to -7.43) 3 Why aragonite not calcite? • Organisms which calcify internally and externally – Internal calcifiers tend to secrete calcite – External calcifiers tend to secrete aragonite • Freshwater water environments do not secrete aragonite but rather calcite • The mineralogy or inorganic cements and of different groups has changed through time Folk 1974 4 Why aragonite? • Has to do with the Mg/Ca ratio; present day the molar ratio is 5:1 • Several hypotheses – The high Mg favors the formation of HMC which is actually more soluble than aragonite – Mg poisons the side ward growth of crystals forming the acicular habit – Calcite growth is prevented by the obstructive presence of hydrated Mg ions 5 Cohen and McConnaughey (2005) 6 Suggested Titles • The Geological Record of Biomineralization • Models of Biomineralization – Coelenterates – Molluscs – Foraminifera –Procaryotes – Other • Trace Elements • Stable Isotopes References • Biogeochemical cycling of mineral-froming elements, Trudinger and Swaine, Elsevier,1979 • Biomineralization, Dove, De Yoreo, Weiner, MSA, 2003 • Biomineralization 7.